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Sample Exercise 15.

1 Writing Equilibrium-Constant Expressions


Write the equilibrium expression for Kc for the following reactions:

Solution
Analyze: We are given three equations and are asked to write an equilibrium-constant expression for each.
Plan: Using the law of mass action, we write each expression as a quotient having the product concentration
terms in the numerator and the reactant concentration terms in the denominator. Each concentration term is
raised to the power of its coefficient in the balanced chemical equation.

Practice Exercise

Chemistry: The Central Science, Eleventh Edition


By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.2 Converting between Kc and Kp


In the synthesis of ammonia from nitrogen and hydrogen,
Kc = 9.60 at 300 C. Calculate Kp for this reaction at this temperature.
Solution
Analyze: We are given Kc for a reaction and asked to calculate Kp.
Plan: The relationship between Kc and Kp is given by Equation 15.14. To apply that equation, we must
determine n by comparing the number of moles of product with the number of moles of reactants
(Equation 15.15).
Solve: There are two moles of gaseous products (2 NH3) and four moles of gaseous reactants (1 N2 + 3 H2).
Therefore, n = 2 4 = 2. (Remember that functions are always based on products minus reactants.) The
temperature, T, is 273 + 300 = 573 K. The value for the ideal-gas constant, R, is 0.0821 L-atm/mol-K. Using
Kc = 9.60, we therefore have

Practice Exercise

Chemistry: The Central Science, Eleventh Edition


By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.3 Interpreting the Magnitude of an Equilibrium Constant


The following diagrams represent three different systems at equilibrium, all in the same size containers. (a)
Without doing any calculations, rank the three systems in order of increasing equilibrium constant, Kc. (b) If
the volume of the containers is 1.0 L and each sphere represents 0.10 mol, calculate Kc for each system.

Solution
Analyze: We are first asked to judge the relative magnitudes of three equilibrium constants and then to
calculate them.
Plan: (a) The more product that is present at equilibrium, relative to the reactant, the greater the equilibrium
constant. (b) The equilibrium constant is given by the concentrations of products over reactants.

Chemistry: The Central Science, Eleventh Edition


By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.3 Interpreting the Magnitude of an Equilibrium Constant


Solution (continued)
Solve:
(a) Each box contains 10 spheres. The amount of product in each varies as follows: (i) 6, (ii) 1, (iii) 8. Thus,
the equilibrium constant varies in the order (ii) < (i) < (iii).
(b) In (i) we have 0.60 mol/L product and 0.40 mol/L reactant, giving Kc = 0.60/0.40 = 1.5. (You will get
the same result by merely dividing the number of spheres of each kind: 6 spheres/4 spheres = 1.5.) In (ii) we
have 0.10 mol/L product and 0.90 mol/L reactant, giving Kc = 0.10/0.90 = 0.11 (or 1 sphere/9 spheres =
0.11). In (ii) we have 0.80 mol/L product and 0.29 mol/L reactant, giving Kc = 0.80/0.20 = 4.0
(or 8 spheres/2 spheres = 4.0). These calculations verify the order in (a).
Comment: Imagine that there was a drawing, like those above, that represents a reaction with a very small
or very large value of Kc. For example, what would the drawing look like if Kc = 1 105? In that case there
would need to be 100,000 reactant molecules for only 1 product molecule. But then, that would be
impractical to draw.
Practice Exercise

Chemistry: The Central Science, Eleventh Edition


By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.4 Evaluating an Equilibrium Constant When an Equation is


Reversed
The equilibrium constant for the reaction of N2 with O2 to form NO equals Kc = 1 1030 at 25 C:

Using this information, write the equilibrium constant expression and calculate the equilibrium constant for
the following reaction:

Solution
Analyze: We are asked to write the equilibrium-constant expression for a reaction and to determine the
value of Kc given the chemical equation and equilibrium constant for the reverse reaction.
Plan: The equilibrium-constant expression is a quotient of products over reactants, each raised to a power
equal to its coefficient in the balanced equation. The value of the equilibrium constant is the reciprocal of
that for the reverse reaction.
Solve:
Writing products over reactants, we have
Both the equilibrium-constant expression and the
numerical value of the equilibrium constant are the
reciprocals of those for the formation of NO from N2
and O2:
Comment: Regardless of the way we express the equilibrium among NO, N2, and O2, at 25 C it lies on the side
that favors N2 and O2. Thus, the equilibrium mixture will contain mostly N2 and O2, with very little NO present.
Chemistry: The Central Science, Eleventh Edition
By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.4 Evaluating an Equilibrium Constant When an Equation is


Reversed
Practice Exercise

Chemistry: The Central Science, Eleventh Edition


By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.5 Combining Equilibrium Expressions


Given the following information,

determine the value of Kc for the reaction

Solution
Analyze: We are given two equilibrium equations and the corresponding equilibrium constants and are
asked to determine the equilibrium constant for a third equation, which is related to the first two.
Plan: We cannot simply add the first two equations to get the third. Instead, we need to determine how to
manipulate the equations to come up with the steps that will add to give us the desired equation.
Solve: If we multiply the first equation
by 2 and make the corresponding
change to its equilibrium constant
(raising to the power 2), we get

Chemistry: The Central Science, Eleventh Edition


By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.5 Combining Equilibrium Expressions


Solution (continued)
Reversing the second equation and
again making the corresponding change
to its equilibrium constant (taking the
reciprocal) gives
Now we have two equations that sum to
give the net equation, and we can
multiply the individual Kc values to get
the desired equilibrium constant.

Practice Exercise

Chemistry: The Central Science, Eleventh Edition


By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.6 Writing Equilibrium-Constant Expressions for


Heterogeneous Reactions
Write the equilibrium-constant expression for Kc for each of the following reactions:

Solution
Analyze: We are given two chemical equations, both for heterogeneous equilibria, and asked to write the
corresponding equilibrium-constant expressions.
Plan: We use the law of mass action, remembering to omit any pure solids, pure liquids, and solvents from
the expressions.
Solve:
(a) The equilibrium-constant expression is

Because H2O appears in the reaction as a pure liquid, its concentration does not appear in the equilibriumconstant expression.
(b) The equilibrium-constant expression is

Because SnO2 and Sn are both pure solids, their concentrations do not appear in the equilibrium-constant
expression.
Chemistry: The Central Science, Eleventh Edition
By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.6 Writing Equilibrium-Constant Expressions for


Heterogeneous Reactions
Practice Exercise

Chemistry: The Central Science, Eleventh Edition


By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.7 Analyzing a Heterogeneous Equilibrium

Solution
Analyze: We are asked which of several combinations of species can establish an equilibrium between
calcium carbonate and its decomposition products, calcium oxide and carbon dioxide.
Plan: For equilibrium to be achieved, it must be possible for both the forward process and the reverse
process to occur. For the forward process to occur, there must be some calcium carbonate present. For the
reverse process to occur, there must be both calcium oxide and carbon dioxide. In both cases, either the
necessary compounds may be present initially, or they may be formed by reaction of the other species.
Solve: Equilibrium can be reached in all cases except (c) as long as sufficient quantities
of solids are present. (a) CaCO3 simply decomposes, forming CaO(s) and CO2(g) until the equilibrium
pressure of CO2 is attained. There must be enough CaCO3, however, to allow the CO2 pressure to reach
equilibrium. (b) CO2 continues to combine with CaO until the partial pressure of the CO2 decreases to the
equilibrium value. (c) There is no CaO present, so equilibrium cannot be attained because there is no way
the CO2 pressure can decrease to its equilibrium value (which would require some of the CO2 to react with
CaO). (d) The situation is essentially the same as in (a): CaCO3 decomposes until equilibrium is attained.
The presence of CaO initially makes no difference.

Chemistry: The Central Science, Eleventh Edition


By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.7 Analyzing a Heterogeneous Equilibrium


Practice Exercise

Chemistry: The Central Science, Eleventh Edition


By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.8 Calculating K When All Equilibrium Concentrations


Are Known
A mixture of hydrogen and nitrogen in a reaction vessel is allowed to attain equilibrium at 472 C. The
equilibrium mixture of gases was analyzed and found to contain 7.38 atm H2, 2.46 atm N2, and 0.166 atm
NH3. From these data, calculate the equilibrium constant Kp for the reaction

Solution
Analyze: We are given a balanced equation and equilibrium partial pressures and are asked to calculate the
value of the equilibrium constant.
Plan: Using the balanced equation, we write the equilibrium-constant expression. We then substitute the
equilibrium partial pressures into the expression and solve for Kp.
Solve:

Practice Exercise
An aqueous solution of acetic acid is found to have the following equilibrium concentrations at 25 C:
[HC2H3O2] = 1.65 102 M; [H+] = 5.44 104 M; and [C2H3O2] = 5.44 104 M. Calculate the equilibrium
constant Kc for the ionization of acetic acid at 25 C. The reaction is
Answer: 1.79 105

Chemistry: The Central Science, Eleventh Edition


By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.9 Calculating K from Initial and Equilibrium Concentrations


A closed system initially containing 1.000 103 M H2 and 2.000 103 M I2 at 448 C is allowed to reach
equilibrium. Analysis of the equilibrium mixture shows that the concentration of HI is 1.87 103 M.
Calculate Kc at 448 C for the reaction taking place, which is

Solution
Analyze: We are given the initial concentrations of H2 and l2 and the equilibrium concentration of HI. We
are asked to calculate the equilibrium constant Kc for
Plan: We construct a table to find equilibrium concentrations of all species and then use the equilibrium
concentrations to calculate the equilibrium constant.
Solve: First, we tabulate the initial and
equilibrium concentrations of as many
species as we can. We also provide
space in our table for listing the
changes in concentrations. As shown, it
is convenient to use the chemical
equation as the heading for the table.
Second, we calculate the change in
concentration of HI, which is the
difference between the equilibrium
values and the initial values:

Chemistry: The Central Science, Eleventh Edition


By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.9 Calculating K from Initial and Equilibrium Concentrations


Solution (continued)
Third, we use the coefficients in the
balanced equation to relate the change
in [HI] to the changes in [H2] and [I2]:

Fourth, we calculate the equilibrium


concentrations of H2 and I2, using the
initial concentrations and the changes.
The equilibrium concentration equals
the initial concentration minus that
consumed:
The completed table now looks like this
(with equilibrium concentrations in blue
for emphasis):

Notice that the entries for the changes are negative when a reactant is consumed and positive when a product
is formed.
Chemistry: The Central Science, Eleventh Edition
By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.9 Calculating K from Initial and Equilibrium Concentrations


Solution (continued)
Finally, now that we know the
equilibrium concentration of each
reactant and product, we can use the
equilibrium-constant expression to
calculate the equilibrium constant.
Comment: The same method can be applied to gaseous equilibrium problems to calculate Kp, in which case
partial pressures are used as table entries in place of molar concentrations.
Practice Exercise
Sulfur trioxide decomposes at high temperature in a sealed container:
Initially, the vessel is charged at 1000 K with SO3(g) at a partial pressure of 0.500 atm. At equilibrium the SO3
partial pressure is 0.200 atm. Calculate the value of Kp at 1000 K.
Answer: 0.338

Chemistry: The Central Science, Eleventh Edition


By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.10 Predicting the Direction of Approach to Equilibrium


At 448 C the equilibrium constant Kc for the reaction
is 50.5. Predict in which direction the reaction will proceed to reach equilibrium at 448 C if we start with
2.0 102 mol of HI, 1.0 102 mol of H2, and 3.0 102 mol of I2 in a 2.00-L container.
Solution
Analyze: We are given a volume and initial molar amounts of the species in a reaction and asked to
determine in which direction the reaction must proceed to achieve equilibrium.
Plan: We can determine the starting concentration of each species in the reaction mixture. We can then
substitute the starting concentrations into the equilibrium-constant expression to calculate the reaction
quotient, Qc. Comparing the magnitudes of the equilibrium constant, which is given, and the reaction
quotient will tell us in which direction the reaction will proceed.
Solve: The initial concentrations are

The reaction quotient is therefore

Because Qc < Kc, the concentration of HI must increase and the concentrations of H2 and I2 must decrease to
reach equilibrium; the reaction will proceed from left to right as it moves toward equilibrium.
Chemistry: The Central Science, Eleventh Edition
By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.10 Predicting the Direction of Approach to Equilibrium


Practice Exercise

Chemistry: The Central Science, Eleventh Edition


By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.11 Calculating Equilibrium Concentrations

Solution
Analyze: We are given an equilibrium constant, Kp, and the equilibrium partial pressures of two of the three
substances in the equation (N2 and H2), and we are asked to calculate the equilibrium partial pressure for the
third substance (NH3).
Plan: We can set Kp equal to the equilibrium-constant expression and substitute in the partial pressures that
we know. Then we can solve for the only unknown in the equation.
Solve: We tabulate the equilibrium
pressures as follows:

Because we do not know the


equilibrium pressure of NH3, we
represent it with a variable, x. At
equilibrium the pressures must satisfy
the equilibrium-constant expression:
We now rearrange the equation to solve
for x:
Comment: We can always check our
answer by using it to recalculate the
value of the equilibrium constant:
Chemistry: The Central Science, Eleventh Edition
By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.11 Calculating Equilibrium Concentrations


Practice Exercise
At 500 K the reaction
has Kp = 0.497. In an equilibrium mixture at 500 K, the
partial pressure of PCl5 is 0.860 atm and that of PCl3 is 0.350 atm. What is the partial pressure of Cl2 in the
equilibrium mixture?
Answer: 1.22 atm

Chemistry: The Central Science, Eleventh Edition


By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.12 Calculating Equilibrium Concentrations from


Initial Concentrations
A 1.000-L flask is filled with 1.000 mol of H2 and 2.000 mol of I2 at 448 C. The value of the equilibrium
constant Kc for the reaction
at 448 C is 50.5. What are the equilibrium concentrations of H2, I2, and HI in moles per liter?
Solution
Analyze: We are given the volume of a container, an equilibrium constant, and starting amounts of reactants
in the container and are asked to calculate the equilibrium concentrations of all species.
Plan: In this case we are not given any of the equilibrium concentrations. We must develop some
relationships that relate the initial concentrations to those at equilibrium. The procedure is similar in many
regards to that outlined in Sample Exercise 15.9, where we calculated an equilibrium constant using initial
concentrations.
Solve: First, we note the initial
concentrations of H2 and I2 in the
1.000-L flask:
Second, we construct a table in which
we tabulate the initial concentrations:

Chemistry: The Central Science, Eleventh Edition


By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.12 Calculating Equilibrium Concentrations from


Initial Concentrations
Solution (continued)
Third, we use the stoichiometry of the
reaction to determine the changes in
concentration that occur as the reaction
proceeds to equilibrium. The
concentrations of H2 and I2 will
decrease as equilibrium is established
and that of HI will increase. Lets
represent the change in concentration of
H2 by the variable x. The balanced
chemical equation tells us the
relationship between the changes in the
concentrations of the three gases:
Fourth, we use the initial concentrations
and the changes in concentrations, as
dictated by stoichiometry, to express
the equilibrium concentrations. With all
our entries, our table now looks like
this:

Chemistry: The Central Science, Eleventh Edition


By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.12 Calculating Equilibrium Concentrations from


Initial Concentrations
Solution (continued)
Fifth, we substitute the equilibrium
concentrations into the equilibriumconstant expression and solve for the
unknown, x:
If you have an equation-solving
calculator, you can solve this equation
directly for x. If not, expand this
expression to obtain a quadratic
equation in x:
Solving the quadratic equation
(Appendix A.3) leads to two solutions
for x:
When we substitute x = 2.323 into the
expressions for the equilibrium
concentrations, we find negative
concentrations of H2 and I2. Because a
negative concentration is not
chemically meaningful, we reject this
solution. We then use x = 0.935 to find
the equilibrium concentrations:
Chemistry: The Central Science, Eleventh Edition
By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.12 Calculating Equilibrium Concentrations from


Initial Concentrations
Solution (continued)
Check: We can check our solution by
putting these numbers into the
equilibrium-constant expression to
assure that we correctly calculate the
equilibrium constant:
Comment: Whenever you use a quadratic equation to solve an equilibrium problem, one of the solutions will
not be chemically meaningful and should be rejected.
Practice Exercise

Chemistry: The Central Science, Eleventh Edition


By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.13 Using Le Chteliers Principal to Predict shifts in


Equilibrium
Consider the equilibrium

In which direction will the equilibrium shift when (a) N2O4 is added, (b) NO2 is removed, (c) the total
pressure is increased by addition of N2(g), (d) the volume is increased, (e) the temperature is decreased?
Solution
Analyze: We are given a series of changes to be made to a system at equilibrium and are asked to predict
what effect each change will have on the position of the equilibrium.
Plan: Le Chteliers principle can be used to determine the effects of each of these changes.
Solve:
(a) The system will adjust to decrease the concentration of the added N2O4, so the equilibrium shifts to the
right, in the direction of products.
(b) The system will adjust to the removal of NO2 by shifting to the side that produces more NO2; thus, the
equilibrium shifts to the right.
(c) Adding N2 will increase the total pressure of the system, but N2 is not involved in the reaction. The
partial pressures of NO2 and N2O4 are therefore unchanged, and there is no shift in the position of the
equilibrium.
(d) If the volume is increased, the system will shift in the direction that occupies a larger volume (more gas
molecules); thus, the equilibrium shifts to the right. (This is the opposite of the effect observed in Figure
15.13, where the volume was decreased.)
(e) The reaction is endothermic, so we can imagine heat as a reagent on the reactant side of the equation.
Decreasing the temperature will shift the equilibrium in the direction that produces heat, so the equilibrium
shifts to the left, toward the formation of more N2O4. Note that only this last change also affects the value of
the equilibrium constant, K.
Chemistry: The Central Science, Eleventh Edition
By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.13 Using Le Chteliers Principal to Predict shifts in


Equilibrium
Practice Exercise
For the reaction

in which direction will the equilibrium shift when (a) Cl2(g) is removed, (b) the temperature is decreased, (c)
the volume of the reaction system is increased, (d) PCl3(g) is added?
Answer: (a) right, (b) left, (c) right, (d) left

Chemistry: The Central Science, Eleventh Edition


By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.14 Predicting the Effect of Temperature on K


(a) Using the standard heat of formation data in Appendix C, determine the standard
enthalpy change for the reaction

(b) Determine how the equilibrium constant for this reaction should change with temperature.
Solution
Analyze: We are asked to determine the standard enthalpy change of a reaction and how the equilibrium
constant for the reaction varies with temperature.
Plan: (a) We can use standard enthalpies of formation to calculate H for the reaction. (b) We can then
use Le Chteliers principle to determine what effect temperature will have on the equilibrium constant.
Solve:
(a) Recall that the standard enthalpy change for a reaction is given by the sum of the standard molar
enthalpies of formation of the products, each multiplied by its coefficient in the balanced chemical equation,
less the same quantities for the reactants. At 25 C, Hf for NH3(g) is 46.19 kJ/mol. The Hf values for
H2(g) and N2(g) are zero by definition because the enthalpies of formation of the elements in their normal
states at 25 C are defined as zero (Section 5.7). Because 2 mol of NH3 is formed, the total enthalpy change
is

(b) Because the reaction in the forward direction is exothermic, we can consider heat a product of the
reaction. An increase in temperature causes the reaction to shift in the direction of less NH3 and more N2
and H2. This effect is seen in the values for Kp presented in Table 15.2. Notice that Kp changes markedly
with changes in temperature and that it is larger at lower temperatures.
Chemistry: The Central Science, Eleventh Edition
By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Exercise 15.14 Predicting the Effect of Temperature on K


Solution (continued)
Comment: The fact that Kp for the formation of NH3 from N2 and H2 decreases with increasing temperature
is a matter of great practical importance. To form NH3 at a reasonable rate requires higher temperatures. At
higher temperatures, however, the equilibrium constant is smaller, and so the percentage conversion to NH3
is smaller. To compensate for this, higher pressures are needed because high pressure favors NH3 formation.
Practice Exercise
Using the thermodynamic data in Appendix C, determine the enthalpy change for the reaction

Use this result to determine how the equilibrium constant for the reaction should change with temperature.
Answer: H = 508.3 kJ; the equilibrium constant will increase with increasing temperature

Chemistry: The Central Science, Eleventh Edition


By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Integrative Exercise Putting Concepts Together


At temperatures near 800 C, steam passed over hot coke (a form of carbon obtained from coal) reacts to form
CO and H2:
The mixture of gases that results is an important industrial fuel called water gas. (a) At 800 C the equilibrium
constant for this reaction is Kp = 14.1. What are the equilibrium partial pressures of H2O, CO, and H2 in the
equilibrium mixture at this temperature if we start with solid carbon and 0.100 mol of H2O in a 1.00-L vessel?
(b) What is the minimum amount of carbon required to achieve equilibrium under these conditions? (c) What
is the total pressure in the vessel at equilibrium? (d) At 25 C the value of Kp for this reaction is 1.7 1021. Is
the reaction exothermic or endothermic? (e) To produce the maximum amount of CO and H2 at equilibrium,
should the pressure of the system be increased or decreased?
Solution
(a) To determine the equilibrium partial pressures, we use the ideal gas equation, first determining the
starting partial pressure of hydrogen.

Chemistry: The Central Science, Eleventh Edition


By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Integrative Exercise Putting Concepts Together


Solution (continued)
We then construct a table of starting partial pressures and their changes as equilibrium is achieved:

There are no entries in the table under C(s) because the reactant, being a solid, does not appear in the
equilibrium-constant expression. Substituting the equilibrium partial pressures of the other species into the
equilibrium-constant expression for the reaction gives

Multiplying through by the denominator gives a quadratic equation in x:

Chemistry: The Central Science, Eleventh Edition


By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

Sample Integrative Exercise Putting Concepts Together


Solution (continued)

(b) Part (a) shows that x = 6.14 atm of H2O must react for the system to achieve
equilibrium. We can use the ideal-gas equation to convert this partial pressure into a
mole amount.

Thus, 0.0697 mol of H2O and the same amount of C must react to achieve equilibrium. As a result, there
must be at least 0.0697 mol of C (0.836 g C) present among the reactants at the start of the reaction.
(c) The total pressure in the vessel at equilibrium is simply the sum of the equilibrium partial pressures:

(d) In discussing Le Chteliers principle, we saw that endothermic reactions exhibit an increase in Kp with
increasing temperature. Because the equilibrium constant for this reaction increases as temperature
increases, the reaction must be endothermic. From the enthalpies of formation given in Appendix C, we can
verify our prediction by calculating the enthalpy change for the reaction,
H = Hf(CO) + Hf(H2) H (C) Hf(H2O) = +131.3 kJ. The positive sign for H indicates that
the reaction is endothermic.
(e) According to Le Chteliers principle, a decrease in the pressure causes a gaseous equilibrium to shift
toward the side of the equation with the greater number of moles of gas. In this case there are two moles of
gas on the product side and only one on the reactant side. Therefore, the pressure should be reduced to
maximize the yield of the CO and H2.
Chemistry: The Central Science, Eleventh Edition
By Theodore E. Brown, H. Eugene LeMay, Bruce E. Bursten, and Catherine J. Murphy
With contributions from Patrick Woodward

Copyright 2009 by Pearson Education, Inc.


Upper Saddle River, New Jersey 07458
All rights reserved.

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